Procedure for olefin dehydrogenation



' June 11, 1946. 5 SUMERFQRD 2,401,846

PROCEDURE FR OLEFIN DEHYDROGENATION I Filed Dec. 22, 1945 REACTOR HEATING Coll.

H EATING COIL LUTADIBNE EECQVEP-Y Simpson. .0. Sumerfom men/Kw v Q I Patented June 11, 1946 PROCEDURE FOR OLEFIN DEHYDRO- GENATION Simpson D. Sumerford, Baton Rouge, La., asslgnor to Standard Oil Development Com any, a corporation of Delaware Application December 22, 1943, Serial No. 515,218

Claims. (Cl. 260-880) This invention relates to the novel features hereinafter described in the specification and claims, more particularly it relates to a method for improving dehydrogenation catalysts.

It is a matter of record to dehydrogenate butane or butenes to form butadiene. At the present time it appears that butane is best dehydrogenated in two stages to form butadiene; first, a dehydrogenation operation using a dehydrogenation catalyst to form butene, followed by a second dehydrogenation using catalyst consisting of iron oxidesupported on a suitable base and promoted with a compound of an alkali metal, particularly potassium oxide. It has been known for some time that the dehydrogenation of butenes such as butene-2 to form butadiene was an operation whose selectivity wasdiillcult -to maintain at a high level due to the tendency of the nascent butadiene to polymerize. At first this difliculty was counteracted by operating at very low pressures, that is, pressures of 100 mm. of mercury or lower. v

In a large scale commercial plant it is diflicult and expensive to operate in this manner. It has been suggested previously that the difliculty of maintaining a low pressure on the butadiene freshly formed could be overcome by diluting with steam in amounts up to twentyvolumes of steam per volume of reactant, whereupon when the total gas pressure in the zone was one atmosphere the partial pressure of the nascent butadiene would be below 100 mm. and the tendency to polymerize would be effectively counteracted. But

. unfortunately most of the dehydrogenation cat aiysts are aiIected adversely by steam. The researches of Kenneth K. Kearby led to the discovery of a class of catalysts which is insensitive to steam and at the same time is active in the dehydrogenation of butene to butadiene. A full description of these catalysts and the method of using them is given in the application of said Kearby, Serial No. 430,873, filed February 14, 1942.

My present invention has to do with improvements in dehydrogenatin butenes, employing a catalyst of the type described and claimed in' the aforesaid Kearby application, under conditions such as to improve the operation of the catalyst, all of which will subsequently fully appear hereinafter.

The main object of my present invention has to do with improvements in the catalytic dehydrogenation o1 n-butenes, particularly in the presence of steam, to form butadiene. More particularly, my invention has to do with the catalytic dehydrogenation of n-butenes and has for its ob- Ject the accomplishment of increased yields and higher selectivity. Other and further objects of my present invention will appear in the following more detailed description.

In brief compass, my present invention relates to pretreating the dehydrogenation catalyst with natural gas and steam during the period when the catalyst is being brdught up to reaction period from a, cold start, and my researches have indicated that this pretreatment causes a higher initial activity than with steam catalyst pretreatment alone. In other words, prior to my invention in order to activate a catalyst of the type indicated it has been customary to treat the catalyst first with steam. To cite a specific example, a catalyst composed of the following components in parts by weight was employed:

Per cent FerOa 19 M 72 CuO L 4.5 K20 4.5

This catalyst is supported on a grid 2; n-butene is introduced into the system through line I and passed through a heating coil i0, where its temperature is raised to say 900-1100 F. Simultaneously, steam enters the present system through line i2 and is superheated in I l to a temperature of i200 F. The steam and n-butene are then mixed in a feed line 20 and discharged into the top of the reactor, thereafter they flow through the reactor contacting the catalyst and are with drawn through line '22. I The product comprising a mixture of butadiene.' n.-butene-and steamin line 22 is'cooled and solvent treatedin known I manner which need not be discussed herein for its details are known to those familiar with the art. Ihave simply illustrated in the drawing suillcient of the conventional process to afford a better understanding of my invention, and it will be recognized that numerous expedients may be resorted to to improve the operation such as those, for instance, disclosed in the application of Carl Kleiber et al., Serial No. 488.636, flled'May actor, the purpose of the steam being to regenerate the catalyst, for the productive phase of the operation results in the formation of deposits on the catalyst. Thus, the process continues usually on alternate productive and regeneration phases of about one hour duration each. Of course these phases may be extended for more than an hour or may be less than an hour, but usually as indicated they are of about one hour's duration. v It is also pointed out that during the regeneration phase a small amountof oxygen may be mixed with the steam to aid in the regeneration,

. I have found by laboratory test made under the same conditions except on the pretreat that instead of merely treating the catalyst with steam Pretreat Cycle Conv. Yield Selectivity Steamonly lb 80.6 23.0 76 28 3.8 24.0 83

In 28 cycles after using steam and methane in during the intial heating-up period better results the ratio of 12:1 during the heatingvup period, I

secured the results below:

Pretreat Cycle Oonv. Yield Selectivity l a 21.0 21. s 81 Steam-F87], CH4 15 34. 8 26. 2 76 2a 20. s 24. 1 s4 Comparing the results from the runs made identically except for the difference in the pretreat. it will be noted at the beginning of the operation, namely, during cycle 3, the operation was better from the standpoint of conversion and yield where steam was mixed with methane during the pretreating or activation phase. The comparison of the tables shows that the catalyst had a better initial activity and was not characterized by an induction period of low activity which at times has been known to last for several days. The tables also show by reference to cycles 15 and 26 that the operation was better after the induction period from the standpoint of conversion'and yield where steam and methane were used to activate the catalyst.

With,regard to pilot plant operation, results obtained without pretreatment of catalyst with natural gas compared with data-obtained after activation of the catalyst with natural gas and steam show an improvement similar to'that steam and which contains an active oxide. I.

believe, although I do not wish to be bound by any theory, that in the normal activation (using steam only) of such catalysts there is some danger of overoxidi'zing the active catalyst. This is evidenced by the lower initial activity cf'the catalyst particularly,'althoug h it also is observed in the more aged catalyst. In any event, I have found that by activating the catalyst with a mix- 'ture of steam and natural gas, or steam and methane, or steam and any normally gaseous paraflin I improve the operation of the catalyst. It is to be understood that my process is applicable to the use of other catalysts such as iron oxide supported on alumina, or any active oxide supported on a carrier base: particularly one which is capable of existing in more than one valence.

Numerous 'modifications of my invention will appear to those who are familiar with this art. For example, the process described hereinbefore for the dehydrogenation of butene is applicable to styrene production by dehydrogenation of ethyl benzene, i. e., employing the same catalyst, temperature and pressure conditions, etc. In fact, the process is applicable to the dehydrogenation of any saturated alkyl radical containing at least two carbon atoms attached to an aromatic nucleus, as well as to the dehydrogenation of mono-olefinic hydrocarbons, generally.

What I claim is: X

1. In the preparation of dioleflns by catalytic dehydrogenation of oleflns with a steam resistant catalyst in the presence of steam, the step which comprises activating the catalyst prior to the dehydrogenation stage by passing a' mixture of steam and a normally gaseous paraflin hydrocarbon in contact with the catalyst.

2. Method according to claim 1, in. which the hydrocarbon constitutes from 5 to 50% of the steam-hydrocarbon mixture. 4

3. The method set forth in claim 1, in which the olefin to be dehydrognated is n-butenc,

4. Themethod of claim 1, in which the catalyst consists of iron oxide supported on magnesium oxide and contains a promoter.

iron oxide and supported on a carrier, activating the catalyst by pretreating with steam and natural .gas, charging a mixture of steam and nbutene to the reaction zone maintained at a temperature within the range of 1100-1300 E, periodically discontinuing the feed of butene to the bed of catalyst, and feeding steam to the bed of catalyst to regenerate the same.

'6. In the catalytic dehydrogenation of hydrocarbons of the class consisting of mono-olefins and alkylated aromatics containing at least-two carbon atoms in the side chain with a steam resistant catalyst, the step which comprises activating the catalyst prior to the dehydrogenation stage by passing a mixture of steam and a normally gaseous paraflln hydrocarbon in contact with the catalyst.

' 7. The process specified in claim 6 in which I I ethyl benzene is dehydrogenated to form styrene. 8. The process of claim 6 in which the catalyst contains a preponderance of iron oxide,a prothe catalyst. V

SIMPSON D; SUMERFORD. 

